Treatment of materials made of or containing cellulose derivatives



Patented -Aug. 30, 1932 UNET T GEORGE HOLLAND ELLIS, OF SPONDON,

NEAR DERBY, ENGLAND, ASSIGNOR TO CELANESE CORPORATION 015 AMERICA, ACORPORATION OF DELAWARE TREATMENT OF MATERIALS MADE OF OR CONTAININGCELLULOSE DERIVATIVES No Drawing. Application filed October 26, 1928,Serial No. 315,345, and. in Great Britain November 28, 1927.

10 and p-toluene sulpho-chlorid'e, or made of or containing celluloseethers, such for instance as methyl, ethyl or benzyl cellulose or thecorresponding condensation products of cellulose and glycols or otherpolyhydric alcohols,

15 all of which cellulose derivatives are hereinafter referred to asorganic substitution derivatives of cellulose According to the presentinvention materials made of or containing cellulose acetate 0 or otherorganic substitution derivatives of cellulose are treated with alkalinesolutions of zinc, solutions of sodium or potassium zincates being verysuitable.

Materials treated according to the present invention are found to haveabsorbed a considerable proportion of metallic radicle. most probably aszinc oxide which is presumably in a hydrated form and to have-acquiredan increased resistance to hot treatments such as ironing.

The greatest advantage accruing from the present invention, moreespecially with materials made of or containing cellulose esters, isthat the materials treated exhibit an affinity for a very wide varietyof coloring matters. Thus not only do cellulose ester materials sotreated retain their afiinity for basic colors and for the insolublecolors especially devised for application thereto and usually applied assuch in solubilized or dispersed form, e. g. the S. R. A. colors, butthey also exhibit an affinity for the direct cotton colors, for mordantcolors both synthetic and natural, and for the indigoid andanthraquinone vat colors.

The process of the present invention may be carried out at any suitabletemperature, hot or cold, and with any suitable concentration of thealkaline solutions. The process may be conducted continuously bymechanical impregnation, the materialsbeing then allowed time to absorbthe necessary quantity of alkaline solution, or it may be carried out bya simple immersion in the bath or by any other suitable method. Theimmersion method appears to give the best results.

Absorption of the alkaline solutions may i be assisted by addition ofswelling agents for the cellulose derivatives, for example thiocyanates,particularly of the alkali metals or ammonium.

It is further found that the treatment of the materials with alkalinesolutions of zinc enables the production thereon of discharge effects,which hitherto have been difficult of attainment on these materials. Theinvention accordingly further comprises the production of dischargeeffects on materials made of or containing cellulose acetate or otherorganic substitution derivatives of cellulose treated with alkalinesolutions of zinc, for example alkali 'zincates, either by dyeing,printing or otherwise coloring with dischargeable dyestuffs andsubsequently applying discharges as required, or by applying dischargesat selected places and subs'e quently dyeing or otherwise coloring withthe dischargeable dyestuffs. Qolored d scharges may be employedcontamlng llIldlS- chargeable colors.

The discharges employed may be the ordinary reduction discharges, forexample formaldehyde-sulphoxylate or formaldehydehydrosulphite or thelike, or they may be 0x1- dation discharges, for example the chloratedischarges, used with or without accelerators or catalysts, for examplesalts of iron or vanadium. In the case of discharging vat and sulphurcolors, the reduction discharges maybe applied together with leucotropicbodies, that'is to say substances capable of combining with the leucocompound of the dyestufi forming a soluble or more soluble body andthereby facilitating washing out.

The simple reduction discharges may be applied, for example, fordischarging direct cotton dyestuffs or insoluble dischargeable azodyestuffs which'have been applied in dispersed form. Together with theleucotropic bodies referred to above they. may be applied fordischarging indigoid and anthraquinone vat colors and sulphur colors.The oxidation discharges, for instance chlorates, may be applied for thedischarge of diand tri-aryl methane, thiazine, oxazine (includinggallocyanines) azine, azo, xanthene and indigoid dyestufis, as well asmany of the insoluble dyestuffs which are applied in the dispersed form.

The dyestuffs and the discharges (whether applied before or after thedyestuffs) may be applied by any suitable dyeing, printing,

' stencilling or other method.

yarns or threads, containing organic substi- -tion zinc 24.23% sodium35.06%.

are then lifted carefully, rinsed, and 'given' tution derivatives ofcellulose which have been treated with alkaline solutions of zinc, withother yarns or threads, for example wool or silk which may bedeleteriously affected by the alkaline solutions,and thereafter dyeingwith or without discharging.

The following examples are illustrative of the processes of'theinvention, but are not to be regarded as limitingit.

\ Example 1 Cellulose acetate wovenfabric is immersed for 1 hour in acold solution containing 50 grams per litre of sodium zincate ofcomposia light soaping for 15 minutes in 4% soap solution at 45 C. Thefabric so treated is distinguished by its greater resistance to ironingthan that of the untreated fabric; and by its affinity for'basic,mordant, acid and direct cotton dyestuffs.

Ea'ample 2 Cellulose acetate woven fabric is passed 1 continuouslythrough a pad mangle or other suitable machine containing a solution of200 grams per litre of sodium zincate of analysis given in Example 1;the bath tem erature being 25 C. After batching or '3 hours, the fabricis washed thoroughly in cold water, soaped in 4 soap solution for 15minutes at. 45 C. rinsed well and dried or otherwise treated as desired.The fabric is sllmliar to that treated according to Exam- P 9 Example 3A fabric composed of cellulose acetate The goods yarn, after treatingwith alkaline zincate according to the above examples, is dyed with 1%of its weight of Chlorazol Violet R; (Colour Index 388). The material isthen dried and further prepared for printing as desired. It is thenprinted by roller print-' ing machine or hand-block with a printingpaste composed as follows 5 10 grams gum arabic 1: 1 180 grams CaledonJade Green paste (Golour Index 1101). 36 grams sodium hydrosulphite 86grams caustic soda 120 grams anthraquinone 10% paste 108 gramsmethylated spirit I Heat to reduce, cool partly and add 180 gramsformosul (sodiumformaldehyde sulphoxylate) After printing, the materialis dried and steamed in the cottage steamer for 3 to 4 minutes withsteam at 5 lbs. pressure, or alternatively given a passage through therapid ager. at 100"" C. after which-it is given a treatment for 5minutes at 60 C. in an oxidizing bath composed of 2 1 gram per litresodium perborate. 1 gram per litre soap.

After oxidation the fabric is washed, soaped and otherwise treated andfinished as desired or requisite.

Example]; I w A fabric composed of cellulose acetate yarns, which hasbeen treated with alkaline zincate according to Examples 1 or 2 above isdyed with 0.5% of its Weight of i-nitro- 2 methoxybenzeneaZo-diethylaniline, after which the material is dried and furtherfinished for printing as desired. It is then printed on a rollerprinting machine or by hand-block with the following printing paste.

720 grams gum arabic 1}: 1 120 grams anthraquinone 10% paste 60 gramszinc oxide 100 grams Water 200 grams formosul (sodium formaldehydesulphoxylate) After printing, the fabric is dried and steamed in thecottage steamer for 5 to 7 minutes with steam at 5 lbs. pressure orgiven one or two passages through the rapid ager at 100 C. The materialis then washed, soaped and otherwise treated and finished as desired orrequisite.

Example 5 fabric composed of cellulose acetate block with a pasteconsisting of 180 grams leucotrope O (dimethylphenylammonium chloride).1020 grams British gum thickening.

After printing, the material is dried and again printed, using a coverroller, with an. anthraquinone vat color paste as follows:

624 grams gum arabic 1: 1. 240 grams Caledon red BN. paste (Colour Index1162). p a 36 grams caustic soda. 60 grams Turkey red oil. 60 gramsmethylated spirit. 36 grams sodium hydrosulphite.

Heat up to reduce, cool and add 144 grams formosul (sodium formaldehydesulphoxylate) 1: 1.

After printing, the material is given a passage through the rapid agerat 100 C. or alternatively given an equivalent steaming of about 4:minutes in the cottage steamer at 5 lbs. pressure, after which it isoxidized in a 5 gram per litre solution of sodium dichromate for 5minutes at 60 C. It is then washed, soaped and otherwise treated andfinished as desired or requisite.

In a similar manner materials containing other cellulose esters, forexample cellulose formate or cellulose propionate, or immunized cotton,or materials containing cellulose ethers, for instance methyl, ethyl, orbenzyl cellulose, may be treated to obtain similar efl'ects.

What I claim and desire to secure by Letters Patent is 1. Process forthe treatment of materials comprising organic substitution derivativesof cellulose, comprising treating the materials with alkaline solutionsof zinc.

2. Process for the treatmentof materials comprising organic substitutionderivatives of cellulose, comprising treating the materials withalkaline solutions of zinc and thereafter coloring the materials.

3. Process for the treatment of materials comprising cellulose esters,comprising treating the materials with solutions of alkali metalzincates.

1. Process for the treatment of materials comprising cellulose esters,comprising treating the materials with solutions of alkali metalzincates and thereafter coloring the materials.

5. Process for the treatment of materials ing the materials withsolutions of alkali metal zincates and thereafter coloring the materialswith dyestuffs normally applied to cotton. v

6. Process for the treatment of materials comprising cellulose esters,comprising treating the materials with solutions of alkali metalzincates and thereafter locally coloring the materials by applyingseparately both discharges and dischargeable dyestuffs.

7. Process for the treatment of materials comprising cellulose acetate,comprising treating the materials with solutions of alkali metalzincates.

8. Process for the treatment of materials comprising cellulose acetate,comprising treatingthe materials with solutions of alkali metal zincatesand thereafter coloring the materials.

9. Process for the treatment of materials comprising cellulose acetate,comprising treating the materials with solutions of alkali metalzincates and thereafter coloring the materials with dyestuffs normallyapplied to cotton.

10. Process for the treatment of materials comprising cellulose acetate,comprising treating the materials with solutions of alkali me'falzincates and thereafter locally coloring the materials by applyingseparately both discharges and dischargeable dyestuffs. 11. Process forthe treatment of materials comprising cellulose acetate, comprisingtreating the materials with solutions of alkali metal zincates andthereafter locally coloring the materials by applying separately bothdischarges and dischargeable dyestuffs normally applied to cotton.

12. Process for the treatment of materials I comprising celluloseacetate, comprising treating the materials with solutions of alkalimetal zincates and thereafter locally coloring the materials byuniformly coloring with dischargeable dyestuffs and thereafter locallyapplying discharges.

13. Process for the treatment of materials comprising cellulose acetate,comprising treating the materials with solutions of alkali metalzincates and thereafter locally coloring the materials by uniformlycoloringwith dischargeable dyestuffs and thereafter locally applyingcolored discharges.

14. Process for the treatment of materials comprising cellulose acetate,comprising treating the materials with solutions of alkali metalzincates and thereafter locally'coloring the materials by uniformlycoloring with dischargeable dyestuffs and thereafter locally applyingreduction discharges. r

15. Process for the treatment of materials comprising cellulose acetate,comprising treating the materials with solutions of alkali metalzincates and thereafter locally coloring the materials by uniformlycoloring with dischargeable dyestuffs and thereafter locally applyingcolored reduction discharges.

QEJ

16. Partially saponified materials comprising cellulose esters andcontaining zinc oxide.

17. Partially saponified colored materials comprising cellulose estersand containing zinc oxide.

18. Partially saponified materials comprising cellulose acetate andcontaining zinc oxide.

19. Partially saponified colored materials comprising cellulose acetateand containing zinc oxide.

In testimony whereof I have hereunto subscribed my name.

GEORGE HOLLAND ELLIS.

